Preparation of uranium hexafluoride



0d 6, 1959` s. LAwRosKl :TAL 2,907,630

PREPARATION OF URANIUM HEXAFLUORIDE Filed Feb. e, 1958 United, States Patent-i0. "GCC to the United States of America as represented by the United States Atomic Energy Commission Application Febrqary 6, 195s, serial N6. 113,173 4 claims. (c1. z3 14.s)l

This invention relates to one" step in a complete process for preparing uranium hexauoride from ore concentrates. In more detail the invention relates to the preparation of uranium hexafluoride from crude uranium tetrafluoride by reacting uranium tetrauoride with fluorine in al fluidized bed. Y

Fluidization may be described briefly as the phenomenon which occurs when a gas passes upwardly through a bed of solid particles at suicient velocity to prevent the particles from remaining in intimate contact with one another. In this condition a certain degree of freedom to move is imparted to the solid particles. In the fluidized state the solid-gas phase behaves much like a liquid having the ability `to ow readily under the influence of a hydrostatic head.

The use of the fluidized bed technique has significant advantages in reactions involving gas and a finely divided solid. 'Ihese advantages may be summarized as follows: (1) the mobility of theiluidized solids permits ready transfer of solids to and from a reaction Vessel, therebyV permittingV continuous'operation; (2) excellent temperature control is obtainable.; (3) high heat transfer coefficients are obtainedpbetween the solid particles and a heating or cooling surface; and (4) high reactionrates .are obtained because of the large surface area of the iluidized particles. l Y l Y Production of uraniumvhexauoride from uranium ores now comprises a multiple step process including leaching the ore, dissolution ofthe ore concentratein nitric acid, purification by solvent extraction, denitration, reduction, hydrofluorination to uranium tetrauoride, and fluorina-V tion to uranium hexailuoride.

A simpler scheme which eliminates the solvent extraction and denitration steps and employs fractional distillation of uranium hexailuoride for purification of uranium can be employed. According to this scheme the ore concentrate .obtained from a leaching step, which is in the heat liberated by the reaction.

z,9o7,63o Patented y Qct. 6, :1959

It is accordingly an object of the present invention to provide a` method for the conversion of uraniumtetrai fiouride to uranium hexailuoride in a uidized bed.

It is a more specific object of the present invention to provide a method of reacting crude uranium tetrailuo'ride, obtained by reduction and hydroiluorination of'ore concentrates, with iluorine in afluidized bed.

These and other objects'of the present invention are accomplished by diluting the uranium tetrailuoride in the bed with at least an equal quantity of an inert diluent to obtain gooduidization characteristics for the uranium tetr-auoride and prevent caking and sintering in the bed. In addition, it is desirable to dilute the iluorine reactant with a gaseous diluent.V

Ihe invention 'will now be described with reference to the accompanying 'drawing which shows a diagrammatic representation of a fluidized bed reactor in which our method can be carried out. Y In the drawing the number 1 denotes the fluidized bed reactor, 2 isa perforated gas diffusion disk, 3 is a metal filter, 4 is a cooling coil, Sis an inlet line for uorine, 6 is an inlet line for a gaseous diluent, 7 is an inlet line for uranium tetrafluoride, 8 is an inlet line for an inert solid diluent, 9 is the off-gas line, 10 is one or a series of cold traps, 11 is an outlet line for noncondensible gases, 12 is the product uranium hexafluoride line, and`13 is an outlet line for solid diluent and ash. Operation of the Y reactor is conventional; uranium tetrafluoride is introduced' into the reactor from the top and fluorine from thebot# tom. The reaction of lluorine with uranium tetrailuoride yields gaseousuranium hexafluoride which is taken off through the offgas line at the top while the ash is removed from theV bottom. Filter 3 is provided to prevent ne solid Iparticles from` being carried into the offgas line.. The product is removed from the off-gas by cold traps 10. Cooling coil 4 is provided to remove the )One of the essential features of the present invention resides in the addition of an inert diluent Ato the bed. One diluent which has been used and found satisfactory is calcium fluoride. The diluent serves a multiplicity of purposes. In the -frst place the diluent is added to form a carrier bed. Since the product of the reaction of uranium tetrauoride With fluor-ine is a gas, most of the materialin the feed will be vapon'zed. The diluent provides a carrier with which the nonvaporized impurities in the feed may be removed from the reactor. In addition,

' presence of the diluent serves to dampen the quite vigform of fine powder, is briquetted, crushed,V and screened orous reaction of uranium tetrauoride with uorine. Because ofthe vigor with which the reaction proceeds most ofthe uranium tetrauoride reacts immediately after it is. fed into thev reactor. It would therefore be difficult to maintain a uniform bed in the reactorwithout the dilcan be conducted successfully on a variety of ore concen-v trates in fluidized bed reactors. For successful operation of the complete process,vit is essential that Athe reaction between uranium tetrauoride and uorine be carried out without any difficulties that would interfere with continous operation of the process. We have found this re-' l action can be carried out on crude uranium tetrafluoride obtained by reduction and hydrofluorination of,o re c on centrates provided certain procedures are followed to as sure good iluidization characteristics of the crude uranium uent. Auniform .bed is of course necessary in order to get uniform uidization of the particles in the bed. For these reasons it is desirable that a diluent be employed y even though compelling reasons for its use are not present.

. A very important consideration in the feasibility of the complete process for the preparation of uranium hexafluoride from ore concentrates resides in the ease with which the product `of the hydrofluorination step can be used directly` in the fluorination'reactor. It is, of course, desirable Afor a. practical commercial process that this material be fed continuously into the fluorination reactor Without any intermediate preparatory steps. It has been found that the source of the uranium tetrailuoride is very important' in this connection. Purified uranium tetrafluoride obtained from other methods of preparation can be. -iluidized easily and can lbe iiuorinated Without a diluent.' For the reasons previously advanced, however,

a diluent-shou1d be used with this material. Uranium tetrafluoridel prepared fromore concentrates differs, radi:L

. 3 cally depending on whether the concentrate was obtained by acid leaching or carbonate leaching.

It has been found `that fit is absolutely essential to employ a diluent with uranium tetrafluoride prepared from a concentrate obtained bythe carbonate-leach method. It is .believed `that the reason for this is the sodium fluoride present in the impure uranium tetrafluoride. Because of they difference in .atomic weights a small amount of sodium iluoride will be suiiicient to compl x a large amount of uranium tetrailuoride. There is .a sufiicient amount of .sodium fluoride present in the -crude uranium -tetrafluoride to complex most of the uranium as a sodium uoride-uranium tetrailuoride complex.

Although theV melting points of sodium iluoride and uranium tetrafluoride are relatively high- 995 C. aand 1030 C., respectively-melting points of various complexes which may be formed are much lower-in the range 600 C. Ito 7.00" C. This lowering of the melting point produces -a corresponding lowering of the sintering temperature. Therefore, the crude uranium tetrafluoride will sinter and cake yat the temperatures present in the reactor if no diluent is present. The `diluent prevents sintering and -caking by separating the particles.

A diluent also improves the fluidization characteristics of uranium tetrafluoride prepared from acid-.leach concentrates. "Ihe fluidization characteristics of the uranium tetrauoride will depend on the source of the ore, the amount and character of impurities in the ore and the size of the particles. By removing particles sized larger than'40 'mesh from some feeds prepared from the acidleach concentrates, a material having good fluidization character is obtained. It is not essential that a diluent be added to lsuch feeds. Other feeds prepared from acidleach lconcentrates have such poor fluidization characteristics that a diluent is essential. `It will be noted that improved results are obtained from adding a diluent to feeds having good iluidization properties so that according vto the present invention a diluent is added even though the fluorination reaction could be carried vout without a diluent.

At .least an yequal :quantity -of diluent is added to the crude uranium 'tetrailuoride Preferably the mixture y'of uranium tetrauoride and diluent should include abou 75% by weight of diluent.

The diluent must be -one that does not introduce impur-ities into the product. Therefore, `a fluoride is indicated. The iluoride must be one which does not react with iluorine. Calcium fluoride and magnesium fluoride of suitable particle size are satisfactory. Crystalline calcium uoride, for example, screend to +100 mesh and having a tapped bulk density of 1.7 gJml. is satisfactory. A mixture of 5 0 lweight percent crude uranium tetratluoride in calcium fluoride fluidized somewhat better than did the uranium tetrauoride alone. A mixture of 75 weight percent calcium uoride iluidized as easily as the calcium uoride alone land there was no caking at the gas distribution disk inthe bottom of the reactor.

The rate iof the reaction is dependent on temperature. 'Ihe satisfactory temperature range lies between '300 and 600 C. .Since caking becomes .substantial over 450 C. the preferred temperature of operation yis about 450 C.-the maximum Iat which operation l'can be carried out without caking. For the more diflicultly iluidizable `carbonate leach feed, the maximum temperature which can be used is .somewhat lower .so that `the range is between 300 .and 450 C. Optimum temperature is near zthe top of this range.

`It is desirable `to introduce .iluorine into the reactor in admixture'with an inert gaseous diluent. The reaction of pure iluorine and uranium -tetrafluoride so vigorous that an jinert diluent is desirable to control the reaction.v

Near the upper limit :of the temperature range uorine will burn in .uranium tetrafluoride. limit of Ithe range pure fluorine can be used. A satisfactory diluent is nitrogen in a mole ration of F2 to N2 of between 0.10 and 0.90. 'Ihe fluorine concentration in the fluidizing gas stream does not aect the iluorine efficiency appreciably, but it does have a strong influence on the rate of uranium hexailuoride production.

Experiments which indicate the desirability and in some cases necessity of empolying an inert diluent will next be ldescribed. v

. The .first .experiments -were carried out-.in a metal tube which was lone inch indameter. A resistance heater was .employed to obtain lthe desired temperatures and no cooling means 1were found necessary. The A'feed was a Rand SouthAfrican ore concentrate reduced and hydrofluorinated in v3`inch ytluidzedbeds at 450 C. The experiments were carried yout on 'crude uranium tetrailuoride with poor fluidization characteristics. 'Iherefore, use off the inert diluent was essential to obtain satisfactory performance of the reactor. Screen analysis `of a typical sample is as follows:

A summary of the results and .a ydescription of the lruns follows: f

TABLE II The ,fiu-ornatz'on yojf crude :uranium vietraluoraie in a onez'nch yludzed .bed reactor Gas stream: 0.073 g./min. 11g-diluted with Nq to give a gas 110W of 1,500 cc./min. in the reactor.

Bed contents: 25 weight percent crude uranium tetratluoride; .75 weight percent CaFg mesh).

'- Initial Bed Composition Fluorine lAddition'Data Stoichio Fluorine Y 1, Crude Bed .metric Y g E111- Run No. Cal", A UFB Temp. Equiva- Time ciencyu (g.) (g.) (O.) 1ents=of (min.) (per- Fluorine cent) Added b 56.2 18.23- 45o 1, 30p 50 450 `1 30. 44 56.2 18.8 450 27 62 Y 450 d 29 62 Y 450 Excess (f) 56 2 18.8 450 l B0 67.5 EB) 450 1 30 68. 8 450 `1 f 30 67. 5 (e) 450 1 30 67.5 l 45o 1v so 65.5 (e) 45o. 1 30 V56.2 k18.8 400 Y 1 20 52.3 300; 1v l3o 45.6 a) 200 1 30 21.5 1 30 Y 10. 3 100 1 30 0. 5 56.2 18. 8 100 1 30 1.05

(e) 150 1f 30- 0.4 200 1 so 12.8 ll) '250 1 30 49.1 e) 300 1 30 49.6 35.0 1 3o 48.6 a) -400 `1 30 46.0 450 1 30 y48. 4 500 l 30 38.3

f Purity 95.4 percent.

position.

1 95% of UF, collected.

Run. 10.-About 94 Apercent of the 'uranium was collected as the hexafluoride. Two stoichiometric equivation.

lents of fluorine Vwere added separately, the collection traps being replaced between the additions.V -During the irst addition the tluorine eiciency wasabout 50 percent.

Run 11.-,-It was demonstrated that practically all the uranium was removed from the bed by the addition of excess iluorine. The stoichiometric equivalent of fluoriue added initially showed anfeiciency of 62 percent. Additionaliluorine, vcorresponding to the uranium tetrafluorideremaining inthe bed, again gave 62 percent eliciency. Excess iluorine was then passed through the bed to remove as much of the uranium as possible. About 9.5 percent` of the uranium was collected as the hexafluoride during the three iluorine additions. y

Run 13.-lt was shown that the lluorination reaction in lthe uidized bed could be operated on asemi-continnous basis to produce about 100 g. of uranium hexafluoride. Nine cycles were carried out, each cycle representing the addition of a stoichiometric equivalent of uorine, andl the addition of enough crudeuranium tetrafluoride to return the bed to its original composi- Fluorinatio Total flow rate: 3146 (za/ruin. Temperature: 450 C.

believed that the uorination was primarily that of uranium tetrauoride untilv fthe temperature had been reduced below 250 C. In run 18 the lluorination was probably that of the,uranium intermediates which had consumed Vpart of the lluorine in their formation. At 250 C. uranium tetrafluoride began to belfluorinated along with the intermediates. The lower values at 500v C. are probably due to caking. e v

Experiments Vwere also carried out with the crude uranium tetrafluoride produced from Anaconda carbonate ore concentrate. It was necessary to screen the sample to -60 mesh in order to attain satisfactory fluidization. Very little uranium hexatluoride was produced from the charge in the reactor. When the reactor was opened, a plug of green sintered material was discovered-.extending for a considerable length'in the one-inch pipe. Due to the sintering tendency exhibited by the carbonate-leach uranium tetrauoride, calcium uoride diluent was added to the Vbed to improve uidization. The results of several experiments are listed in Table III.

TABLE In n of crude carbonate-leach-uranium tetrafuorz'de in a fiuz'dized-bed reactor e Bed contents: carbonate leach-uranium tetrailuorlde (18.8 g.)+75% GaFz Fn En- U Mole ciency, Volatilized 'U Run Ratio, Time Percent with Excess Balance, Remarks (Also see text) No. Fa/Nn (min.) (U Volatil- Fa (Per- Percent zed)/ cent) Y Initial U 27 0.02 48 51.5 64.4 Preliminary experiment. Flow rate 6,292 cc./min. instead of usual 3,146 tze/min. due to unfavorable particle size of the CaFz. Some caking of material in bed.

30 0.04 65 48.4 84.7 90.0 Preliminary experiment. One of the iluorothene tubes containing UF6 ignited in the stream of pure F2. Some caking of material in bed.

33 0.72 35.3 108.8 Large cake about the diam. of the reactor tube present in bed.

34 0. 72 15 20. 8 96.4 Slight caldng of material in bed.

In the first cycle an average lluorine eliiciency of about 67 percent was realized, the highest obtained in any of the runs. At the end of the fth cycle some plugging occurred in the gas distribution plate at the bottom of the bed. The minor difliculties encountered Were believed to result from the design of the small laboratory-scale equipment.

Run 14.--An effort was made to gain a rough indication of the temperature dependence of the reaction. operationally, the procedure was identical to that of run 13, except that the temperature of the bed was varied. A strong temperature effect was shown by the iluorine eiciency, which dropped to 0.5 percent at 100 C.

Run 18.--An additional experiment was performed in which the reactor was operated semi-continuously, the temperature being changed With each addition of uranium tetrailuoride. The operation was similar to that in run 14, except that thetemperature was changed in reverse order with the lower temperatures first, and a 2-inch extension doubling the length of the reactor was used. Both runs agreed in showing Athat the rate of uorination below 250 C. was slow. In run 14, however, the fluorine eflciency increased With temperature, while in run 18 the uorine eiciency was essentially constant in the Z-450 C. range. The differences in the two runs may be explained, at least partially, by work which indicates that the lluorination rate of uranium tetrauoride is about four times as fast as the iluorination of uranium iiuorides intermediate between the tetrailuoride and the hexauoride. In run 14 it is Run 27.-A preliminary experiment using thirty percent more uorine than is stoichiometrically required was performed -to establish whether or not the uranium could be volatilized from the bed by uorination of the carbonate-leach uranium tetrauoride. The high iluidizing velocity required in this experiment may have been at least partially responsible for the low percentage of uranium volatilized; it is suggested that `the reactivity of the carbonate-leach uranium tetrauoride may be less than that of crude uranium tetratluoride from the other sources.

Run 30.-An experiment was performed to determine the approximate fluorine efficiency and the total amount of uranium that could be volatilized. Twenty percent excess uorine was added in the first 30 minutes of the experiment, excess fluorine was added during the next 30 minutes, and pure uorine was added during the iinal 5 minutes of the experiment. Since the main objective of the run was to establish the total amount of uranium that could be Volatilized, the fluorine ethciency was based only on the uranium hexauoride in the cold trap and did not include that held in lines or collected in the sodium hydroxide scrubber. It is estimated, however, that the error in the iluorine eii'iciency should not exceed about 20 percent of the value quoted in the table. Two other operational difliculties may have contributed minor errors in the uranium data. One of the uorothene tubes in the olf-gas line ignited during the run, and some of the bed contents were lost through the gas distribution plate. The results do indicate, however, that better ef- 7 'ciencesand uranium recoverieswerepossible'than those obtained rin the ,previous experiments.

Runs 3'.i3if.-'Il1e purposeof these 'runs wastoche'ck the uorine efciencies using lstoichiornetrically 'equivalentarnounts of Huorine with 'the carbonate-"leach uranium -te'trauoride Although caking and sintering were present, it appeared that this 'material was less Ireactive than that from the other sources.

Run 35.-:'111 was found that a suiciently Vlarge excess of yuorine'would volatilize 'most of the uranium from the "bed A,

It is thus apparent that use of an 'inert diluent makes it possible to uorinate crude uranium Ate'trauoride vin a'udized bed `reactor Wherethe crude uranium tetrauoride'has such characteristics that -it otherwise could not vbesatisfactorily' uorinated in a uidized bed reactor.

In `generali-'it was -found that the carbonate-leach uranium Atetraiuoride was much more diiiicult to handle than that from-the other two sources due to its low sintering temperature and apparent lack of reactivity. By using an easi'ly uidized inert diluent 'and with an optimum choice of conditions, however, it .appears that it can be handledsatisfactorily inailuidizedibed uorination.

Heat removal required no Special arrangements in the laboratory experiments described, .but in .a 4larger scale unit provisions .for Vcooling are necessary.

Uranium hexafluoride obtained by the procedure described has been puriied to a very great extent lover` that present in the ore concentrate. [It requires :further purification, however, before it can be used in a vdiiusion process. This is accomplished by fractional distillation.

It will be understood that this invention is not to be limited 'to the details 'given 'herein butjthat it may be modified within the'sc'ope of 'the v4appended claims.

V`What i's'clairnedis: v '1. A processifor preparing uranium hexauoride from a carbonate-leach concentrateof uranium ore comprising jbri'quetting, crushing and screening the concentrate to `obtain va material suitable :for uidizatiom Yreducing and hydroiiuorinating Ythe concentrate in f iuirdized 'bed reactors, fluorinating the resulting crude uranium tetrauoride in admixture with at least Aan equal quantity of an inert Ysolid diluent in auiluidized lbed reactor, and purifying the resulting `uranium hexauoride by 'fractional distillation.

2. The process of claim 1 .wherein vthe inert solid diluent is calcium fluoride.

3. yThe process of claim 2 wherein the fluorination is carried out by introducing the 'uorine vinto the bed in admixture with an inert gaseous diluent.

4. The process lof claim '3 'wherein'the Yinert gaseous diluent is nitrogen.

References Cited in the le of this patent UNITED STATES PATENTS 

1. A PROCESS FOR PREPARING URANIUM HEXAFLUORIDE FROM A CARBONATE-LEACH CONCENTRATE OF URANIUM ORE COMPRISING BRIQUETTING, CRUSHING AND SCREENING THE CONCENTRATE TO OBTAIN A MATERIAL SUITABLE FOR FLUIDIZATION, REDUCING AN HYDROFLUORINATING THE CONCENTRATE IN FLUIDIZED BED REACTORS, FLUORINATING THE RESULTING CRUDE URANIUM TETRAFLUORIDE IN ADMIXTURE WITH AT LEAST AN EQUAL QUANTITY OF AN INERT SOLID DILUENT IN A FLUIDIZED BED REACTOR, AND 